Cyclometalated Iridium Complexes from Intramolecular C–H Activation of [IrCp*Cl{C(OMe)CHC(CH₃)R}L] (R = CH₃, Ph; L = PPh₂Me, PMe₃)

The (methoxy)­alkenylcarbeneiridium complexes [IrCp*Cl­{C­(OMe)­CHCR¹R²}­L]­PF₆ (R¹ = CH₃, R² = CH₃, Ph; R¹ = Ph, R²= H; L = PPh₂Me, PMe₃) can undergo an intramolecular C–H activation of one of the substituents R of the alkenyl fragment to give new five-membered-ring cyclometalated iridium complexes. In this work it is shown that the arrangement of substituents in the alkenyl fragment determines the size of the ring in the iridacycle complexes. The iridacyclopenta-1,3-diene complexes [IrCp*­{C­(OMe)­CHCRCH₂}­L]­PF₆ (L = PPh₂Me, R = CH₃ (<b>2a</b>), Ph (<b>4a</b>); L = PMe₃, R = CH₃ (<b>2b</b>), Ph (<b>4b</b>)) can be deprotonated to give the iridacyclopenta-2,4-diene complexes [IrCp*­{C­(OMe)CHCRCH}­L] (L = PPh₂Me, R = CH₃ (<b>6a</b>), Ph (<b>7a</b>); L = PMe₃, R = CH₃ (<b>6b</b>), Ph (<b>7b</b>))

Cyclometalated Iridium Complexes from Intramolecular C–H Activation of [IrCp*Cl{C(OMe)CHC(CH₃)R}L] (R = CH₃, Ph; L = PPh₂Me, PMe₃)

The (methoxy)­alkenylcarbeneiridium complexes [IrCp*Cl­{C­(OMe)­CHCR¹R²}­L]­PF₆ (R¹ = CH₃, R² = CH₃, Ph; R¹ = Ph, R²= H; L = PPh₂Me, PMe₃) can undergo an intramolecular C–H activation of one of the substituents R of the alkenyl fragment to give new five-membered-ring cyclometalated iridium complexes. In this work it is shown that the arrangement of substituents in the alkenyl fragment determines the size of the ring in the iridacycle complexes. The iridacyclopenta-1,3-diene complexes [IrCp*­{C­(OMe)­CHCRCH₂}­L]­PF₆ (L = PPh₂Me, R = CH₃ (<b>2a</b>), Ph (<b>4a</b>); L = PMe₃, R = CH₃ (<b>2b</b>), Ph (<b>4b</b>)) can be deprotonated to give the iridacyclopenta-2,4-diene complexes [IrCp*­{C­(OMe)CHCRCH}­L] (L = PPh₂Me, R = CH₃ (<b>6a</b>), Ph (<b>7a</b>); L = PMe₃, R = CH₃ (<b>6b</b>), Ph (<b>7b</b>))

Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp³)–Oxygen Bond versus Aminolysis

The iridium methoxycarbene [IrCp*Cl­{C­(OMe)­CHCPh₂}­(PPh₂Me)]­PF₆ (<b>3</b>) can undergo a clean attack by nucleophiles at least by two different pathways: (1) an unusual nucleophilic attack of primary, secondary, and tertiary amines at the sp³ carbon–oxygen bond, which gives an acyl complex and amine alkylation and (2) a nucleophilic attack of the ammonia at the carbenic carbon, which forms a primary aminocarbene

Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp³)–Oxygen Bond versus Aminolysis

The iridium methoxycarbene [IrCp*Cl­{C­(OMe)­CHCPh₂}­(PPh₂Me)]­PF₆ (<b>3</b>) can undergo a clean attack by nucleophiles at least by two different pathways: (1) an unusual nucleophilic attack of primary, secondary, and tertiary amines at the sp³ carbon–oxygen bond, which gives an acyl complex and amine alkylation and (2) a nucleophilic attack of the ammonia at the carbenic carbon, which forms a primary aminocarbene

Formation of Indanone from an Iridanaphthalene Complex

The first example of evolution of an iridanaphthalene into an indanone through an intermediate indenyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C–H activation of a phenyl ring of a carbene ligand in [IrCp*­{C­(OMe)­CHCPh₂}­(L)]­PF₆ (L = PPh₂Me, PMe₃) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indenyl complexes and 3-phenylindanone

Formation of Indanone from an Iridanaphthalene Complex

The first example of evolution of an iridanaphthalene into an indanone through an intermediate indenyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C–H activation of a phenyl ring of a carbene ligand in [IrCp*­{C­(OMe)­CHCPh₂}­(L)]­PF₆ (L = PPh₂Me, PMe₃) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indenyl complexes and 3-phenylindanone

Formation of Indanone from an Iridanaphthalene Complex

The first example of evolution of an iridanaphthalene into an indanone through an intermediate indenyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C–H activation of a phenyl ring of a carbene ligand in [IrCp*­{C­(OMe)­CHCPh₂}­(L)]­PF₆ (L = PPh₂Me, PMe₃) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indenyl complexes and 3-phenylindanone

Formation of Indanone from an Iridanaphthalene Complex

The first example of evolution of an iridanaphthalene into an indanone through an intermediate indenyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C–H activation of a phenyl ring of a carbene ligand in [IrCp*­{C­(OMe)­CHCPh₂}­(L)]­PF₆ (L = PPh₂Me, PMe₃) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indenyl complexes and 3-phenylindanone

Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp³)–Oxygen Bond versus Aminolysis

The iridium methoxycarbene [IrCp*Cl­{C­(OMe)­CHCPh₂}­(PPh₂Me)]­PF₆ (<b>3</b>) can undergo a clean attack by nucleophiles at least by two different pathways: (1) an unusual nucleophilic attack of primary, secondary, and tertiary amines at the sp³ carbon–oxygen bond, which gives an acyl complex and amine alkylation and (2) a nucleophilic attack of the ammonia at the carbenic carbon, which forms a primary aminocarbene